Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
  • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
  • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
  • C09D5/024—Emulsion paints including aerosols characterised by the additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
  • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate

Definitions

• the present invention relates to a water-based resin composition. Specifically, the present invention relates to a water-based paint, which is excellent in weather resistance, using the water-based resin composition. Further, the present invention relates to a weather resistance improver for a water-based paint using the water-based resin composition, which can sharply improve weather resistance when added to the water-based paint. Furthermore, the present invention relates to a weather resistance improver for a thermoplastic resin and a weather resistance improver for a solvent-based paint, both of which use a resin composition recovered from the water-based resin composition, and these improvers can sharply improve weather resistance when added to the thermoplastic resin and the solvent-based paint, respectively.
• Patent Document 1 a paint, which is made by copolymerizing an ultraviolet light absorber (hereinafter, expressed as a “reactive UVA”) having an unsaturated double bond, in a molecule, capable of radical polymerization, with a polymerizable monomer having a highly hydrophobic cyclohexyl group, having excellent weather resistance for a long time without showing the bleed out of the UVA component from the coating film can be obtained.
• an ultraviolet light absorber hereinafter, expressed as a “reactive UVA”
• Patent Document 2 there is a description that a paint, which is made by copolymerizing a hindered amine type light stabilizer (hereinafter, expressed as a “reactive HALS”) having an unsaturated double bond in a molecule and a polymerizable monomer having a highly hydrophobic cyclohexyl group, having excellent weather resistance for a long time without showing the bleed out of the HALS component from the coating film can be obtained.
• a paint which is made by copolymerizing a hindered amine type light stabilizer (hereinafter, expressed as a “reactive HALS”) having an unsaturated double bond in a molecule and a polymerizable monomer having a highly hydrophobic cyclohexyl group
• Patent Document 3 there is a description that a paint composed of an emulsion obtained by copolymerizing a reactive HALS at the last stage of a multistage emulsion polymerization in the presence of a silane coupling agent having a cyclohexyl group is excellent in compatibility and film formability, and excellent weather resistance for a long time can be obtained.
• Patent Document 4 a technology has been proposed, in which a nonreactive UVA or a nonreactive HALS which does not have an unsaturated double bond in a molecule is previously dispersed in water using an emulsifier and then the resultant dispersion is added to the water-based paint to improve weather resistance of the water-based paint.
• a weather resistance improver such as HALS, UVA, or an antioxidant in accordance with characteristics of each thermoplastic resin has been proposed.
• HALS high-strength polystyrene
• UVA ultraviolet absorbent
• an antioxidant in accordance with characteristics of each thermoplastic resin.
• the weather resistance improver having relatively low molecular mass it is difficult to maintain capability for improving weather resistance for a long time owing to bleed out of the weather resistance improver with time, which results in concentration lowering of the weather resistance improver in a base material.
• a polymer type weather resistance improver has been proposed.
• Patent Document 5 a technology of improving weather resistance of a thermoplastic resin has been proposed, in which a reactive UVA and a reactive HALS are copolymerized in high concentration in an organic solvent and the resultant mixture is reprecipitated in a poor solvent to recover the polymer type weather resistance improver which is then compounded into the thermoplastic resin.
• Patent Document 1 Japanese Patent Application Laid-Open No. Hei 8-198,130
• Patent Document 2 Japanese Patent No. 2,637,574
• Patent Document 3 Japanese Patent Application Laid-Open No. 2004-10,805
• Patent Document 4 Japanese Patent Publication No. Hei 3-46,506
• Patent Document 5 Japanese Patent Application Laid-Open No. 2003-40,937
• the weather resistance improver was produced by extremely complicated method, in which the weather resistance improver was recovered by reprecipitation after solution polymerization, which caused problems in industrial production. Further, there remained a very small amount of an organic solvent in the recovered material, which caused a problem in the use where control of high-degree odor level was required.
• the present invention has been made in view of the above-mentioned circumstances and a purpose of the present invention is to provide a water-based resin which can be used not only as a water-based paint having high-degree weather resistance but also, when added to another water-based paint, as a weather resistance improver which can drastically improve the weather resistance of the other water-based paint to which the weather resistance improver has been added.
• Another purpose of the present invention is to provide a weather resistance improver which, when added to various thermoplastic resins and solvent-based paints, can improve their weather resistance.
• One aspect of the present invention resides in a water-based resin composition containing a copolymer (A) which is obtained by carrying out emulsion polymerization of an unsaturated monomer composed of 0.5 to 50 parts by mass of an ethylenically unsaturated monomer (a), represented by the following general formula (I), having a piperidyl group in a molecule and 50 to 99.5 parts by mass of an ethylenically unsaturated monomer (b), which does not substantially contain an ethylenically unsaturated monomer having a functional group represented by the following formula (II), (III), or (IV) in a molecule, with the total of the unethylenically unsaturated monomers (a) and (b) being 100 parts by mass, under the coexistence of 0.1 to 10 parts by mass of an emulsifier,
• R 1 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms
• X represents an oxygen atom or an imino group
• Y represents a hydrogen atom or an alkyl or alkoxyl group having 1 to 20 carbon atoms
• Z represents a hydrogen atom or a cyano group.
• Another aspect of the present invention resides in a weather resistance improver for water-based paints and a water-based paint both of which contain the foregoing water-based resin composition.
• Another aspect of the present invention resides in a resin composition obtained by recovering solid matter in the foregoing water-based resin composition.
• Another aspect of the present invention resides in a weather resistance improver for thermoplastic resins and a weather resistance improver for solvent-based paints both of which include the foregoing resin composition.
• the water-based resin composition of the present invention needs to be the one in which the content of an ethylenically unsaturated monomer (a) represented by the general formula (I) is 0.5 to 50 parts by mass, provided that the total amount of the unsaturated monomers at the time of polymerization is 100 parts by mass.
• the content of the ethylenically unsaturated monomer (a) is 0.5 parts by mass or more, weather resistance of a coating film obtained by using the water-based resin composition alone as a water-based paint is largely improved.
• the content of the ethylenically unsaturated monomer (a) needs to be 50 parts by mass or less from the viewpoints of polymerization stability and storage stability.
• the content of the ethylenically unsaturated monomer (a) is preferably 6 to 50 parts by mass in the use in which high-degree pigment dispersibility or designability such as matt is required as a coating film.
• the content of the ethylenically unsaturated monomer (a) is within this range, pigment dispersibility and resin-beads dispersibility can be improved and hence excellent finish can be obtained in the uses of clear paints and paints with various pigments.
• the content of the ethylenically unsaturated monomer (a) is preferably 6 to 50 parts by mass, provided that the total amount of the unsaturated monomers at the time of polymerization is 100 parts by mass, from the viewpoints of compatibility with a polymer which constitutes the other water-based paint to which the weather resistance improver for water-based paints is added and realization of weather resistance of a coating film.
• the weather resistance of the water-based paint can be largely improved without any large changes in physical properties of paint and physical properties of coating film of the water-based paint obtained by adding a small amount of the weather resistance improver for water-based paints.
• the content of the ethylenically unsaturated monomer (a) is more preferably 20 to 50 parts by mass.
• the content of the ethylenically unsaturated monomer (a) is preferably 6 to 50 parts by mass, provided that the total amount of the unsaturated monomers is 100 parts by mass.
• the weather resistance of a thermoplastic resin can be largely improved without any large changes in physical properties and moldability of the thermoplastic resin by adding a small amount of the weather resistance improver for thermoplastic resins to the thermoplastic resin.
• the amount of use of the ethylenically unsaturated monomer (a) is more preferably 20 to 50 parts by mass.
• the content of the ethylenically unsaturated monomer (a) is preferably 6 to 50 parts by mass, provided that the total amount of the unsaturated monomers is 100 parts by mass.
• the weather resistance of a solvent-based paint can be largely improved without any large changes in physical properties of the solvent-based paint and physical properties of the coating film by adding a small amount of the weather resistance improver for solvent-based paints to the solvent-based paint.
• the amount of use of the ethylenically unsaturated monomer (a) is more preferably 20 to 50 parts by mass.
• the one having a stabilizing function for ultraviolet light can be used, and for example, 4-(meth)acryloyloxy-2,2,6,6-tetramethyl piperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethyl piperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, or 4-cyano-4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine can be listed.
• These monomers can be used alone or in combination of two or more kinds when it is needed.
• a methacrylate monomer in which R 1 in the general formula (I) is a methyl group is used alone or in combination of two or more kinds as the ethylenically unsaturated monomer (a)
• a drastic improving effect on weather resistance can be obtained in the case that the water-based resin composition of the present invention is used as the weather resistance improver for water-based paints, and, therefore, the methacrylate is preferable.
• An ethylenically unsaturated monomer (b) is the one which does not substantially contain an ethylenically unsaturated monomer having an acidic functional group represented by the formula (II), (III), or (IV) in a molecule (hereinafter, expressed as an “acid monomer”).
• the expression “does not substantially contain an ethylenically unsaturated monomer” means that the content of the ethylenically unsaturated monomer is less than 0.1%.
• the ethylenically unsaturated monomer (b) does not substantially contain the acid monomer, stability of emulsion polymerization is largely improved. Further, lowering of diffusibility and radical scavenging capability of a HALS component caused by mutual interaction of the acidic functional group and the HALS component in a coating film can be suppressed.
• an alkyl (meth)acrylate having an alkyl group with 1 to 12 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl acrylate, n-amyl (meth)acrylate, i-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate,
• a (meth)acrylate type unsaturated monomer is preferably used from the viewpoint of weather resistance of the water-based resin.
• the water-based resin composition of the present invention is used as a weather resistance improver for water-based paints
• main monomers which give the water-based paints, alone or in combination of two or more kinds, in accordance with the water-based paints to which the weather resistance improver is added from the viewpoint of maintaining various characteristics of the water-based paints.
• a (meth)acrylate type unsaturated monomer from the viewpoint of improving weather resistance of the water-based paints containing the weather resistance improver for water-based paints of the present invention.
• thermoplastic resins or a weather resistance improver for solvent-based paints it is preferable to use main monomers, which constitute the thermoplastic resins or the solvent-based paints, alone or in combination of two or more kinds, in accordance with the kinds of the thermoplastic resins or the solvent-based paints to which the weather resistance improver is added from the viewpoint of improving various characteristics of the thermoplastic resins or the solvent-based paints.
• the water-based resin composition of the present invention is used as a water-based paint, a weather resistance improver for water-based paints, a weather resistance improver for thermoplastic resins or a weather resistance improver for solvent-based paints, deterioration of a resin and a HALS component can be suppressed and weather resistance or capability for improving weather resistance can be improved in any of the above uses, in the case that an unsaturated monomer having an ultraviolet light absorbing group represented by the following general formula (V), (VI), or (VII) in a molecule (hereinafter, expressed as a “reactive UVA”) is used as one component of the ethylenically unsaturated monomer (b).
• an unsaturated monomer having an ultraviolet light absorbing group represented by the following general formula (V), (VI), or (VII) in a molecule hereinafter, expressed as a “reactive UVA”
• the reactive UVA when a large amount of the reactive UVA is copolymerized, there is a case that polymerization stability in an emulsion polymerization is lowered or that transparency of a coating film is lowered. Consequently, when the reactive UVA is used as one component of the ethylenically unsaturated monomer (b), it is preferable that the reactive UVA be copolymerized in an optimum range in accordance with the use of the water-based resin composition of the present invention.
• the amount of the reactive UVA is preferably 2 parts by mass or less to 100 parts by mass of the total amount of the unsaturated monomers at the time of polymerization.
• the amount of the reactive UVA is 2 parts by mass or less, yellowness of a coating film is low and a coating film realizing high-degree weather resistance can be obtained.
• the amount of the reactive UVA is preferably within the range of from 5 to 20 parts by mass, provided that the total amount of the unsaturated monomers at the time of polymerization is 100 parts by mass.
• the amount of the reactive UVA is 5 parts by mass or more, sufficient effects on absorbing ultraviolet light and on improving weather resistance of the paint to which the water-based resin composition has been added can be obtained with a small amount of addition of the water-based resin composition, without changing various properties of the paint.
• the amount of the reactive UVA is 20 parts by mass or less, polymerization stability can be secured, and moreover, coloring of the coating film of the paint to which the water-based resin composition has been added can be evaded.
• mass average molecular mass (Mw) of the copolymer (A) is particularly preferably within the range of from 5,000 to 300,000.
• Mw mass average molecular mass
• diffusibility of the UVA component is improved and coloring property of the coating film is further improved in the course of forming films of the water-based paints to which the weather resistance improver for water-based paints of the present invention is added.
• the mass average molecular mass (Mw) is 5,000 or more, bleed out of the UVA component from the coating film can be suppressed and capability for improving weather resistance for a long time can be given.
• the most preferable mass average molecular mass of the copolymer (A) is from 5,000 to 200,000.
• the amount of the reactive UVA is preferably 20 parts by mass or less, provided that the total amount of the unsaturated monomers at the time of polymerization is 100 parts by mass.
• the amount of the reactive UVA is 20 parts by mass or less, sufficient polymerization stability can be obtained.
• R 2 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms
• R 3 represents a linear or a branched hydrocarbon substituted group having 1 to 15 carbon atoms or a hydrocarbon substituted group having a cyclic structure
• R 4 represents a linear or a branched hydrocarbon substituted group having 1 to 25 carbon atoms or a hydrocarbon group having a cyclic structure.
• R 5 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms
• R 6 represents a linear or a branched hydrocarbon substituted group having 1 to 15 carbon atoms or a hydrocarbon substituted group having a cyclic structure
• R 7 represents a linear or a branched hydrocarbon substituted group having 1 to 25 carbon atoms or a hydrocarbon group having a cyclic structure.
• R 8 represents a hydrogen atom or a methyl group
• R 9 to R 12 independently represent a hydrogen atom or a linear alkyl group having 1 to 10 carbon atoms, respectively.
• the water-based resin composition of the present invention has to be subjected to emulsion polymerization in the presence of 0.1 to 10 parts by mass of an emulsifier to 100 parts by mass of the total amount of the unsaturated monomers at the time of polymerization.
• an emulsifier to 100 parts by mass of the total amount of the unsaturated monomers at the time of polymerization.
• the amount of the emulsifier is 0.1 parts by mass or more, polymerization stability and mechanical stability are improved.
• the amount of the emulsifier is 10 parts by mass or less, water resistance of a coating film is not lowered in the case that the water-based resin composition of the present invention is used as a water-based paint or a weather resistance improver for water-based paints.
• the amount of the emulsifier is preferably 1 part by mass or more in point of polymerization stability. Further, in order to give further high-degree water resistance to the coating film, the amount of the emulsifier to be used is preferably 8 parts by mass or less.
• emulsifiers to be used conventionally known various anion or nonion emulsifiers, or polymer emulsifiers, or the like can be listed. Further, when a reactive emulsifier having a radical polymerizable unsaturated double bond in a molecule is used, higher-degree water resistance and weather resistance can be given to the coating film in the case that the water-based resin composition of the present invention is used as a water-based paint or a weather resistance improver for water-based paints.
• a reactive anion emulsifier as the emulsifier.
• a reactive anion emulsifier in the case of the use in which, in particular, high mechanical stability is needed, it is more preferable to jointly use a reactive anion emulsifier and a reactive nonion emulsifier.
• the ratio of the reactive anion emulsifier to the reactive nonion emulsifier is particularly preferably 8/2 to 2/8 (mass ratio).
• the unsaturated monomer of the present invention does not contain the reactive emulsifier.
• an anion emulsifier such as “Newcol 560SF”, “Newcol 562SF”, “Newcol 707SF”, “Newcol 707SN”, “Newcol 714SF”, “Newcol 723SF”, “Newcol 740SF”, “Newcol 2308SF”, “Newcol 2320SN”, “Newcol 1305SN”, “Newcol 271A”, “Newcol 271 NH”, “Newcol 210”, “Newcol 220”, “Newcol RA331”, or “Newcol RA332” (each one is a trade name and manufactured by Nippon Nyukazai Co., Ltd.), “Latemul B-118E”, “Levenol WZ”, or “Neopelex GI 5” (each one is a trade name and manufactured by Kao Corporation), or “Hightenol N08” (a trade name and manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), or an anion emulsifier such as “Nonipol
• polyvinyl alcohol polyhydroxyethyl (meth)acrylate, polyhydroxypropyl (meth)acrylate, or poly(vinylpyrrolidone) can be listed.
• a reactive anion emulsifier such as “Antox MS-60” or “Antox MS-2N” (each one is a trade name and manufactured by Nippon Nyukazai Co., Ltd.), “Eleminol JS-2” (a trade name and manufactured by Sanyo Chemical Industries, Ltd.), “Latemul S-120”, “Latemul S-180”, “Latemul S-180A”, or “Latemul PD-104” (each one is a trade name and manufactured by Kao Corporation), “Adeka Reasoap SR-10” or “Adeka Reasoap SE-10” (each one is a trade name and manufactured by Asahi Denka Kogyo K.K.), “Aquaron KH-05”, “Aquaron KH-10”, or “Aquaron HS-10” (each one is a trade name and manufactured by Dai-ichi Kogyo Seiyaku Co.
• the water-based resin composition of the present invention may have a crosslinked structure or a noncrosslinked structure, however, it has preferably a noncrosslinked structure or a low-crosslinked structure, and particularly preferably a noncrosslinked structure.
• the water-based resin composition of the present invention is used as a weather resistance improver for water-based paints or in the case that a resin composition recovered from the water-based resin composition is used as a weather resistance improver for thermoplastic resins
• improving effect on weather resistance can be realized in a wider range of water-based paints or thermoplastic resins because diffusibility of a HALS component to the resin to which the HALS component is added is improved by making the water-based resin composition or the resin composition have a noncrosslinked structure or a low-crosslinked structure.
• a weather resistance improver for solvent-based paints it is preferable for a weather resistance improver for solvent-based paints to have a noncrosslinked structure.
• polymerization under the coexistence of a chain transfer agent is also effective as well as a method of increasing the amount of an initiator.
• a chain transfer agent it is preferable to carry out emulsion polymerization of the unsaturated monomers in the presence of 0.1 to 10 parts by mass of the chain transfer agent to 100 parts by mass of the total amount of the unsaturated monomers at the time of polymerization.
• the amount of the chain transfer agent is 0.1 parts by mass or more, crosslinking density can be lowered.
• the amount of the chain transfer agent exceeds 10 parts by mass, it is not preferable because a large amount of the unreacted chain transfer agent remains in the polymer thus obtained and Mw is drastically lowered.
• the more preferable range of the amount of the chain transfer agent is 0.1 to 5 parts by mass in point of resistance to bleed out and weather resistance.
• chain transfer agent a publicly known chain transfer agent like a mercaptan-based chain transfer agent such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan, or n-butyl mercaptan; a halogen compound such as tetrachlorocarbon, or bromoethylene; a disulfide compound such as diphenyl disulfide; or ⁇ -methylstyrene dimer can be used. These agents can be used alone or in combination of two or more kinds.
• mass average molecular mass (hereinafter, expressed as “Mw”) of the copolymer (A) constituting the water-based resin composition of the present invention is not particularly limited, however, it is preferably within the range of from 5,000 to 300,000 in accordance with the use of the water-based resin composition of the present invention.
• Mw mass average molecular mass of the copolymer (A) constituting the water-based resin composition of the present invention.
• Mw mass average molecular mass of the copolymer (A) constituting the water-based resin composition of the present invention
• the Mw of the copolymer (A) is 5,000 or more, bleed out of the copolymer (A) from the coating film obtained by forming a water-based paint containing the weather resistance improver for water-based paints of the present invention into a film can be suppressed and a weather resistance over a long period of time can be held.
• the Mw of the copolymer (A) is 300,000 or less, diffusibility of the HALS component in a film forming process is improved in the case that the weather resistance improver for water-based paints of the present invention is added to water-based paints in a wide range, and as a result, capability for improving weather resistance of the weather resistance improver for water-based paints and weather resistance of the coating film composed of the water-based paint to which the weather resistance improver is added are improved.
• the Mw of the copolymer (A) is preferably within the range of from 5,000 to 300,000 because of the same reason as [that] in the case of the weather resistance improver for water-based paints.
• the Mw of the copolymer (A) is preferably 20,000 or more, and more preferably within the range of from 20,000 to 300,000.
• the Mw of the copolymer (A) is 20,000 or more, weather resistance of the coating film can maintain sufficient weather resistance.
• the Mw of the copolymer (A) is 300,000 or less, film formability is further improved and high water resistance and weather resistance can be obtained.
• the more preferable Mw of the copolymer (A) is within the range of from 50,000 to 300,000.
• the minimum film forming temperature (hereinafter, expressed as “MFT”) measured by the method according to “JIS K 6828 5.11” is preferably 70° C. or below.
• MFT minimum film forming temperature
• the water-based resin composition when used as the weather resistance improver for water-based paints, it is apprehended that sufficient diffusibility of the HALS component cannot be obtained in the course of a film forming process of the water-based paint containing the weather resistance improver for water-based paints of the present invention, and weather resistance cannot be sufficiently improved with regard to the resultant coating film.
• the most preferable MFT is 50° C. or below.
• the glass transition temperature (hereinafter, expressed as “Tg”) of the copolymer (A) which constitutes the water-based resin composition of the present invention is not particularly limited, however, it is preferable to change the Tg in accordance with the use of the water-based resin composition.
• the Tg of the copolymer (A) is preferably 100° C. or below. When the Tg of the copolymer (A) is 100° C.
• the water-based paint containing the water-based resin composition of the present invention has good film formability and does not lower water resistance or weather resistance of the resultant coating film.
• the Tg of the copolymer (A) is preferably 70° C. or below, and more preferably 50° C. or below. Further, in the case that the water-based resin composition of the present invention is used as a weather resistance improver for thermoplastic resins, the Tg of the copolymer (A) is preferably 50° C. or above. When the Tg of the copolymer (A) is 50° C.
• the Tg of the copolymer (A) is more preferably 70° C. or above.
• a multistage polymerization be adopted at the time of emulsion polymerization and a copolymer having a high Tg be formed at the outermost layer in point of powder characteristics.
• a calculated glass transition temperature obtained by the Fox equation is used.
• the Fox equation is a relation equation of a glass transition temperature (° C.) of a copolymer and glass transition temperatures (° C.) of homopolymers obtained by independently homopolymerizing respective comonomers of the copolymer as shown below.
• 1/(273 +Tg ) ⁇ ( Wi /(273 +Tgi )) (in the above equation, Wi represents a mass ratio of a monomer i and Tgi represents a Tg (° C.) of a homopolymer of the monomer i.)
• Tg of each homopolymer concretely, the values described in “Polymer Handbook 3rd Edition” (Wiley-Interscience Publication, 1989) can be used.
• the water-based resin composition of the present invention can be produced, for example, by emulsion polymerization with a radical polymerization initiator using the ethylenically unsaturated monomer (a), the ethylenically unsaturated monomer (b), and an emulsifier in a water medium.
• the particle structure of the copolymer (A) constituting the water-based resin composition of the present invention may be a monolayered structure or a multilayered structure, however, in the case of the multilayered structure, a three-layered structure or less is preferable from the viewpoints of production efficiency and particle diameter control.
• the multilayered structure it may be carried out, for example, to polymerize the ethylenically unsaturated monomer (b) in the first step and then polymerize the mixture of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) in the second step or later or to polymerize the mixture of the ethylenically unsaturated monomers (a) and (b) in the first step and then polymerize the ethylenically unsaturated monomer (b) in the second step or later.
• the concentration of the ethylenically unsaturated monomer (a) in each step is preferably 50 parts by mass or less, provided that the total amount of the monomers in respective steps is 100 parts by mass.
• concentration of the ethylenically unsaturated monomer (a) exceeds 50 parts by mass in each step, polymerization stability of the step is lowered, and it is not preferable.
• the one to be generally used in a radical polymerization can be used, a concrete example of which includes a persulfate such as potassium persulfate, sodium persulfate, or ammonium persulfate; an oil-soluble azo compound such as azobisisobutyronitrile, 2,2′-azobis(2-methyl butyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), or 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; a water-soluble azo compound such as 2,2′-azobis ⁇ 2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide ⁇ , 2,2′-azobis ⁇ 2-methyl-N-[2-(1-hydroxyethyl)]propionamide ⁇ ,
• initiators can be used alone or in combination of two or more kinds. Further, when promotion of polymerization speed or polymerization at low temperature, namely 70° C. or below, is desired, it is advantageous to jointly use a reducing agent, for example, sodium bisulfite, ferrous sulfate, or an ascorbate and a radical polymerization catalyst.
• a reducing agent for example, sodium bisulfite, ferrous sulfate, or an ascorbate
• the amount of addition of the radical polymerization initiator is usually within the range of from 0.01 to 10 parts by mass to the total amount of ethylenically unsaturated monomers, and is particularly preferably 0.05 to 5 parts by mass in consideration of progress of the polymerization or control of the reaction.
• the particle diameter of the polymer particle constituting the water-based resin composition of the present invention is not particularly limited, however, it is preferable to select the optimum particle diameter in accordance with the use of the water-based resin composition of the present invention.
• an average particle diameter the one of cumulant analysis obtained by the measurement at 25° C. of the sample which was adjusted to 1% concentration, using “Fiber-Optics Particle Analyzer with Autosampler FPAR-1000” manufactured by Otsuka Electronics Co., Ltd. was adopted.
• the average particle diameter is preferably in the range of from 30 to 200 nm.
• the average particle diameter is 30 nm or more, polymerization stability is improved and hence the amount of an emulsifier to be used, which may be an important factor of lowering of water resistance of the coating film, can be reduced.
• the average particle diameter is 200 nm or less, film formability of the water-based paint is improved and hence various physical properties such as water resistance and weather resistance of the coating film are improved.
• the average particle diameter is preferably in the range of from 30 to 300 nm.
• the average particle diameter is 300 nm or less, diffusibility of the weather resistance improver for water-based paints of the present invention into the coating film is improved and hence high-degree improving performance of weather resistance can be obtained owing to the HALS component diffused in the coating film.
• the average particle diameter it is more preferably 170 nm or less, and particularly preferably 140 nm or less. Further, the average particle diameter is preferably 30 nm or more in order to prevent lowering of water resistance of the coating film caused by an increase in the emulsifier.
• the average particle diameter is preferably 30 nm or more.
• the average particle diameter is 30 nm or more, polymerization stability is improved.
• the solid matter concentration (hereinafter, expressed as “NV”) of the water-based resin composition of the present invention is not particularly limited, however, it is preferably within the range of from 30 to 70 parts by mass.
• NV solid matter concentration
• the water-based resin composition of the present invention is used as a water-based paint, sufficient film formability can be obtained and hence appearance of the coating film is excellent, provided that the NV is 30 parts by mass or more.
• the water-based resin composition of the present invention is used as a weather resistance improver for water-based paints, physical properties of paint of the water-based paint to which the weather resistance improver for water-based paints has been added can be maintained.
• recovery efficiency of the solid matter in the recovery step of the solid matter in the case of using the water-based resin composition of the present invention as a weather resistance improver for thermoplastic resins or a weather resistance improver for solvent-based paints becomes sufficient. Further, when the NV is 70 parts by mass or less, excellent polymerization stability can be obtained.
• stability of the emulsion can be raised by adjusting the pH of the emulsion to become weak alkalinic, namely within the range of from about 7.5 to 10.0, by adding a basic compound after the polymerization.
• ammonia triethylamine, propylamine, dibutylamine, amylamine, 1-aminooctane, 2-(dimethylamino)ethanol, ethylaminoethanol, 2-(diethylamino)ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-(propylamino)ethanol, ethoxypropylamine, aminobenzyl alcohol, morphorin, sodium hydroxide, or potassium hydroxide can be listed.
• an inorganic basic compound in the case of the use such as an interior which is desired not to contain VOC. Further, in the case where even a faint odor is not desired, it is preferable to use a nonvolatile inorganic basic compound such as sodium hydroxide or potassium hydroxide.
• the water-based resin composition of the present invention is used as a water-based paint
• one kind of the water-based paint having the same composition alone or a mixture of two or more kinds of the water-based paints having different compositions may be used.
• various pigments, a film-forming aid, a defoaming agent, a pigment dispersing agent, a leveling agent, an anti-sagging agent, a matting agent, a nonreactive HALS, a nonreactive ultraviolet light absorber, an antioxidant, a heat resistance improver, a slip agent, a viscosity control agent, an antiseptic agent, and the like may be added.
• the water-based paint of the present invention may be used after mixed with a melamine-based hardening agent, an epoxy-based hardening agent, or an isocyanate-based hardening agent of emulsion type, water-soluble resin type, low molecular mass type, or the like.
• a publicly known coating method such as a spray coating method, a roller coating method, a bar coating method, an air-knife coating method, a brush coating method, or a dipping method may be properly selected and carried out.
• the amount of addition of the weather resistance improver for water-based paints in the case that the water-based resin composition of the present invention is used as the weather resistance improver for water-based paints is not particularly limited, however, it is preferably 1 to 50% by mass as solid matter, provided that the sum of solid matter-of the weather resistance improver for water-based paints and solid matter of the water-based paint to which the weather resistance improver for water-based paints has been added is 100% by mass.
• the concentration of the weather resistance improver for water-based paints of the present invention is less than 1% by mass, there is a case that sufficient capability for improving weather resistance of the coating film cannot be realized because the concentration of the ethylenically unsaturated monomer (a) in the coating film becomes low even if the concentration of the ethylenically unsaturated monomer (a) in the copolymer (A) which constitutes the weather resistance improver for water-based paints is sufficiently raised. Further, when the concentration of the weather resistance improver for water-based paints of the present invention is exceeding 50% by mass, the characteristics of the water-based paint containing the weather resistance improver for water-based paints of the present invention tends to be lowered. Further, as the weather resistance improver for water-based paints of the present invention, one kind of a resin having a same composition alone or a combination of two or more kinds of resins having different compositions may be used.
• the weather resistance improver for water-based paints of the present invention can be used for various water-based paints such as an acrylic paint, an acryl-silicone paint, a polyester paint, an urethane paint, a fluorine paint, a vinyl chloride paint and an alkyd paint.
• various pigments in order to realize high-degree performances of the weather resistance improver for water-based paints of the present invention and the water-based paint containing it, various pigments, a film-forming aid, a defoaming agent, a pigment dispersing agent, a leveling agent, an anti-sagging agent, a matting agent, a nonreactive HALS, a nonreactive ultraviolet light absorber, an antioxidant, a heat resistance improver, a slip agent, an antiseptic agent, and the like may be added.
• additives may be added to a mixture obtained after the weather resistance improver for water-based paints of the present invention is added to the water-based paint or to the water-based paint existing before the weather resistance improver for water-based paints is added to the water-based paint. Further, after these additives are added to the weather resistance improver for water-based paints of the present invention, the resultant weather resistance improver for water-based paints containing these additives may be added to the water-based paint.
• a publicly known coating method such as a spray coating method, a roller coating method, a bar coating method, an air-knife coating method, a brush coating method, or a dipping method may be properly selected and carried out.
• a resin composition obtained by recovering solid matter in the water-based resin composition of the present invention is used as a weather resistance improver for thermoplastic resins
• one kind of a resin having a same composition alone or a combination of two or more kinds of resins having different compositions may be used.
• the combination of two or more kinds of resins is used, the solid matter may be recovered after the two or more kinds of resins have been mixed or the respective resin compositions obtained by separately recovering the solid matter may be mixed to use.
• a publicly known method such as a spray-drying method, a coagulation method or a centrifugation method may be used, and it is preferable that the solid matter be recovered by the spray-drying method or the coagulation method.
• a method for recovering the solid matter using the spray-drying method a method in which a water-based resin composition obtained by emulsion polymerization is spray-dried and recovered as powder with a spray dryer under the conditions of an inlet temperature of 120 to 220° C. and an outlet temperature of 40 to 90° C. can be adopted.
• the outlet temperature is preferably 40 to 80° C. in point of disintegrability of a recovered secondary particle to a primary particle, and particularly preferably 40 to 70° C.
• a method for recovering the solid matter using the coagulation method a method in which a water-based resin composition is contacted with a coagulating agent at 30 to 60° C., coagulated while stirred to make a slurry, and the slurry is dehydrated and dried to recover powder can be adopted.
• a coagulating agent for example, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, an organic acid such as formic acid or acetic acid, or an organic salt such as aluminum sulfate, magnesium sulfate, calcium acetate or calcium sulfate can be listed.
• the weather resistance improver for thermoplastic resins of the present invention can be used for thermoplastic resins such as an acrylic resin, a vinyl chloride resin, a polyethylene resin, a polypropylene resin, a polystyrene resin, an ABS resin, a polyamide resin, a polyester resin and a polycarbonate resin, and the amount of addition can be changed in accordance with a target weather resistance.
• the weather resistance improver for thermoplastic resins of the present invention can be molded together with the thermoplastic resin to which it is added by a publicly known molding method such as an injection molding method, an extrusion molding method, a blow molding method, a press molding method, a calendering method, or an inflation molding method.
• the amount of addition of the weather resistance improver for thermoplastic resins of the present invention is not particularly limited, however, it is preferably 0.1 to 50% by mass to 100% by mass of the sum of the weather resistance improver for thermoplastic resins and the thermoplastic resin.
• the amount of addition is less than 0.1% by mass, sufficient capability for improving weather resistance tends to be lowered. Further, when the amount of addition is exceeding 50% by mass, the characteristics of the thermoplastic resin to which the weather resistance improver for thermoplastic resins is added tends to be lowered.
• thermoplastic resins of the present invention In order to realize high-degree performances of the weather resistance improver for thermoplastic resins of the present invention and the thermoplastic resin containing it, a mold release agent, various kinds of pigments, a dye, a flame retardant, an ultraviolet light absorber, an antioxidant, an antiseptic agent, an anti-fungus agent, and the like may be added.
• the amount of addition of the weather resistance improver for solvent-based paints is not particularly limited, however, it is preferably within the range of from 1 to 50% by mass, provided that 100% by mass of the sum of the solid matter of the weather resistance improver for solvent-based paints and the solvent-based paint is 100% by mass.
• the concentration of the weather resistance improver for solvent-based paints of the present invention is 1% by mass or more, weather resistance of the solvent-based paint to which the weather resistance improver for solvent-based paints has been added is largely improved, and when the concentration of the weather resistance improver for solvent-based paints of the present invention is 50% by mass or less, its effect on the physical properties of the solvent-based paint to which the weather resistance improver for solvent-based paints has been added becomes limitative. Further, as the weather resistance improver for solvent-based paints of the present invention, one kind of a resin having a same composition alone or a combination of two or more kinds of resins having different compositions may be used.
• the weather resistance improver for solvent-based paints of the present invention can be used for various solvent-based paints such as an acrylic paint, an acryl-silicone paint, a polyester paint, a urethane paint, a fluorine paint, a vinyl chloride paint and an alkyd paint.
• the kind of the solvent-based paint may be a thermoplastic paint or a thermosetting paint.
• a brightening agent such as aluminum paste or mica; a coloring agent such as titanium oxide, carbon black or quinacridone; a pigment dispersing agent; a hardening agent such as isocyanate, epoxy or melamine; a leveling agent; an anti-sagging agent; a matting agent; a nonreactive HALS; a nonreactive ultraviolet light absorber; a slip agent; or the like may be added.
• additives may be added to a mixture obtained after the weather resistance improver for solvent-based paints of the present invention is added to the solvent-based paint or to the solvent-based paint existing before the weather resistance improver for solvent-based paints is added. Further, after these additives are added to the weather resistance improver for solvent-based paints of the present invention, the resultant weather resistance improver for solvent-based paints containing these additives may be added to the solvent-based paint.
• a publicly known coating method such as a spray coating method, a roller coating method, a bar coating method, an air-knife coating method, a brush painting coating method, or a dipping method may be properly selected and carried out to obtain a dried coating film thickness of about 10 to 200 ⁇ m.
• the water-based resin composition of the present invention is used as a water-based paint
• solid matter content is not particularly limited, however, it is usually used within the range of from 20 to 80% by mass. Further, in this case, one kind of a water-based resin composition having a same composition alone or a combination of two or more kinds of water-based resin compositions having different compositions may be used.
• various pigments In order to realize high-degree performances of the water-based paint of the present invention, various pigments, a film-forming aid, a defoaming agent, a pigment dispersing agent, a leveling agent, an anti-sagging agent, a matting agent, a nonreactive HALS, a nonreactive ultraviolet light absorber, an antioxidant, a heat resistance improver, a slip agent, a viscosity control agent, an antiseptic agent, and the like may be added.
• the water-based paint of the present invention may be used after mixed with a melamine-based hardening agent, an epoxy-based hardening agent, or an isocyanate-based hardening agent of emulsion type, water-soluble resin type, low molecular mass type, or the like.
• a publicly known coating method such as a spray coating method, a roller coating method, a bar coating method, an air-knife coating method, a brush coating method, or a dipping method may be properly selected and carried out.
• MFT Minimum Film Forming Temperature
• MFT of a water-based resin composition was measured for 3 g of the sample by a method according to “JIS K 6828 5.11” using a minimum film forming temperature measuring device manufactured by Takabayashi Rika Co.
• Cullet formed during polymerization was gathered by filtration using a nylon screen and dried in a dryer at 50° C. for 24 hours, and the dried material was weighed and evaluated by the following standard.
• sample solution was measured under the following conditions using “HCL-8120” manufactured by Tosoh Corporation to obtain mass average molecular mass (Mw). In the case that a peak was not detected after the retention time exceeded 20 minutes, it was concluded that the sample solution had become insoluble owing to formation of a crosslinked structure.
• TIPAQUE CR-97 (trade name, manufactured by Ishihara Sangyo Kaisha, Ltd., titanium oxide made by chloride process): 707 g
• “ADEKA COL W-193” (trade name, manufactured by Asahi Dennka Kogyo K.K., pigment dispersing agent): 12 g
• Surfynol DF-58 (trade name, manufactured by Air Products and Chemicals, Inc., defoaming agent): 25 g
• deionized water 256 g were sufficiently mixed, and glass beads were added to the mixture and the pigment was dispersed for 30 minutes using a high-speed disperser, and then the glass beads and the like were filtrated with a 300 mesh nylon screen to obtain a mill base for evaluation (solid content: 71% by mass).
• This clear paint for evaluation was coated on a steel plate treated with zinc phosphate treatment (steel plate treated with “Bondelite #100”, thickness: 0.8 mm, 70 mm ⁇ 150 mm) by spray coating to the extent that the thickness of the dried coating film became 30 ⁇ m, and kept at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for silica-dispersibility evaluation.
• the gloss at 20 degrees was measured using polarized light glossmeter “VG-2000” (trade name) manufactured by Nippon Denshoku Industries Co., Ltd.
• a glass plate was coated with a clear paint using a 8 mil applicator, and dried at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for evaluation of hot water resistance. Subsequently, the coated plate was soaked in water at 50° C. for 1 week. Whitening, swelling and occurrence of blister right after the plate was taken out were checked and judged according to the following standard.
• the clear paint for evaluation was coated on a steel plate treated with zinc phosphate treatment (steel plate treated with “Bondelite #100”, thickness: 0.8 mm, 70 mm ⁇ 150 mm) by spray coating to the extent that the thickness of the dried coating film became 30 ⁇ m, and kept at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for evaluation of weather resistance for clearness.
• This coated plate was cut to plates each having the size of 70 mm ⁇ 50 mm, and the resultant plates were put in “Daipla Metal Weather KU-R4-W” (trade name, manufactured by Daipla Wintes Co., Ltd.) and tested under the conditions of test cycle: 4 hours of irradiation and 4 hours of moisture condensation; UV strength: 85 mW/cm 2 ; black panel temperature: 63° C. at irradiation and 30° C. at moisture condensation; and humidity: 50% RH at irradiation and 96% RH at moisture condensation, respectively.
• the gloss at 60 degrees was measured using polarized light glossmeter “VG-2000” (trade name) manufactured by Nippon Denshoku Industries Co., Ltd.
• the white enamel paint for evaluation was coated on a steel plate treated with zinc phosphate treatment (steel plate treated with “Bondelite #100”, thickness: 0.8 mm, 70 mm ⁇ 150 mm) by spray coating to the extent that the thickness of the dried coating film became 50 ⁇ m, and kept at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for evaluation of pigment dispersibility.
• a value of gloss at 60 degrees of this test plate as an index the following standard was applied for evaluation.
• the gloss at 60 degrees was measured using polarized light glossmeter “VG-2000” (trade name) manufactured by Nippon Denshoku Industries Co. Ltd.
• the white enamel paint for evaluation was coated on a steel plate treated with zinc phosphate treatment (steel plate treated with “Bondelite #100”, thickness: 0.8 mm, 70 mm ⁇ 150 mm) by spray coating to the extent that the thickness of the dried coating film became 50 ⁇ m, and kept at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for evaluation of weather resistance for enamel coating.
• This coated plate was cut to a plate having the size of 70 mm ⁇ 50 mm, and the resultant plate was put in “Daipla Metal Weather KU-R4-W” (trade name, manufactured by Daipla Wintes Co., Ltd.) and tested under the conditions of test cycle: 4 hours of irradiation and 4 hours of moisture condensation; UV strength: 85 MW/cm 2 ; black panel temperature: 63° C. at irradiation and 30° C. at moisture condensation; and humidity: 50% RH at irradiation and 96% RH at moisture condensation.
• VG-2000 polarized light glossmeter
• the temperature of the resultant solution was measured by a thermometer, and after an exothermic peak was observed, the remainder of the emulsion A was dropped by taking 4 hours at the inside temperature of 75° C., and the resultant system was aged for 2 hours at the same inside temperature of 75° C. to polymerize a monomer of the emulsion A and to form a copolymer (A).
• Example 2 The same procedure as in Example 1 was carried out to prepare water-based coating materials using the emulsion A compounded with the rate shown in Tables 1 and 2. The results of evaluation are shown in Tables 1 and 2.
• Example 2 The same procedure as in Example 1 was carried out to start emulsion polymerization using the emulsion A compounded with the rate shown in Table 2, however, coagulated materials were generated at the stage when a seed particle was formed by adding the initiator solution obtained by dissolving 0.1 part of ammonium persulfate (polymerization initiator) into 5 parts of water, and stirring became difficult owing to coagulated materials generated in course of dropping of the remainder of the emulsion A, and hence the polymerization was stopped.
• the initiator solution obtained by dissolving 0.1 part of ammonium persulfate (polymerization initiator) into 5 parts of water
• water-based paints of the present examples are excellent in weather resistance, silica dispersibility, hot water resistance, and pigment dispersibility as well as mechanical stability, storage stability and polymerization stability.
• the water-based paints of the comparative examples are inferior in polymerization stability or storage stability, and at least one characteristics of weather resistance, silica dispersibility, hot water resistance, and pigment dispersibility are insufficient, even if they are polymerizable. Consequently, it is obvious that the water-based paint having excellent polymerization stability, mechanical stability, and storage stability, and satisfying all the characteristics of weather resistance, silica dispersibility, hot water resistance and pigment dispersibility can be provided according to the present invention.
• a water-based resin composition is compounded to a water-based paint of Reference Example 1 to be mentioned later with a fixed rate (shown in a table).
• “CS-12” trade name, manufactured by Chisso Corporation, film forming aid
• “RHEOLATE350” trade name, manufactured by Rheox Inc., thickener
• “Surfynol DF-58” trade name, manufactured by Air Products and Chemicals, Inc., defoaming agent
• the resultant clear paint was coated on a steel plate treated with zinc phosphate treatment (steel plate treated with “Bondelite #100”, thickness: 0.8 mm, 70 mm ⁇ 150 mm) by spray coating to the extent that the thickness of the dried coating film became 50 ⁇ m, and kept at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for the tests of weather resistance and capability for improving weather resistance.
• TIPAQUE CR-97 (trade name, manufactured by Ishihara Sangyo Kaisha, Ltd., titanium oxide made by chloride process): 707 g
• “ADEKA COL W-193” (trade name, manufactured by Asahi Denka Kogyo K.K., pigment dispersing agent): 12 g
• “Surfynol DF-58” (trade name, manufactured by Air Products and Chemicals, Inc., defoaming agent): 25 g
• deionized water 256 g were sufficiently mixed, and glass beads were added to the resultant mixture and dispersion of the pigment was carried out for 30 minutes using a high-speed disperser, and then the glass beads and the like were filtrated with 300 mesh nylon screen to obtain a mill base for evaluation (solid content: 71% by mass).
• the resultant mixture was filtrated again with a 300 mesh nylon screen to obtain a white enamel paint for evaluation having 40% of PWC.
• the resultant white enamel paint was coated on a steel plate treated with zinc phosphate treatment (steel plate treated with “Bondelite #100”, thickness: 0.8 mm, 70 mm ⁇ 150 mm) by spray coating to the extent that the thickness of the dried coating film became 50 ⁇ m, and kept at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for the tests of weather resistance, chalking, capability for improving weather resistance and pigment dispersibility.
• the resultant coated plate for the test was put in a evaluation device “Daipla Metal Weather KU-R4-W” (manufactured by Daipla Wintes Co., Ltd.) and tested under the conditions of test cycle: 4 hours of irradiation and 4 hours of moisture condensation; UV strength: 85 mW/cm 2 ; black panel temperature: 63° C. at irradiation and 30° C. at moisture condensation; and humidity: 50% RH at irradiation and 96% RH at moisture condensation.
• a glass plate was coated with a clear paint using a 8 mil applicator, and dried at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for evaluation of hot water resistance. Subsequently, the coated plate was soaked in water at a room temperature (about 20° C.) for 1 week. Whitening of coating film thus obtained right after the plate was taken out was checked by visual inspection and judged according to the following standard.
• a glass plate was coated with a clear paint using a 8 mil applicator, and dried at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for evaluation of compatibility.
• the state of the coating film was checked by visual inspection and judged according to the following standard.
• a state of chalking of a coating film after an accelerated test of 2,000 hours was evaluated by visual inspection and judged according to the following standard.
• the temperature of the resultant solution was measured by a thermometer, and after an exothermic peak was observed, the remainder of the emulsion A was dropped by taking 4 hours at the inside temperature of 75° C., and the resultant system was aged for 2 hours at the same inside temperature of 75° C. to polymerize a monomer of the emulsion A and to form a copolymer (A).
• Example 2 The same procedure as in Example 1 was carried out to prepare water-based resin compositions using the emulsion A compounded with the rate shown in Tables 3 to 5.
• the temperature of the resultant solution was measured by a thermometer, and after an exothermic peak was observed, the remainder of the emulsion A was dropped by taking 2 hours at the inside temperature of 75° C., and the resultant mixture was aged for 1 hour, and then the emulsion B was dropped by taking 2 hours at the inside temperature of 75° C.
• the resultant system was aged for 2 hours at the same inside temperature of 75° C. to reduce a remaining monomer and to form a copolymer (A). Subsequently, the system was cooled and 28% by mass aqueous ammonia was added at a temperature of 60° C. or below till the pH of the system became 9 to prepare a water-based resin composition.
• Table 7 The results of evaluation are shown in Table 7.
• the temperature of the resultant solution was measured by a thermometer, and after an exothermic peak was observed, the remainder of the emulsion A was dropped by taking 2 hours at the inside temperature of 75° C., and the resultant mixture was aged for 1 hour, and then 28% by mass aqueous ammonia was added till the pH of the system became 4, and the emulsion B was dropped by taking 2 hours at the inside temperature of 75° C. Subsequently, the resultant system was aged for 2 hours at the same inside temperature of 75° C. to reduce a remaining monomer and to form a copolymer (A).
• Example 11 The same procedure as in Example 11 was tried to carry out emulsion polymerization using the emulsion A compounded with the rate shown in Table 4, however, coagulated materials were generated at the stage when a seed particle was formed by adding the initiator solution obtained by dissolving 0.1 part of ammonium persulfate (polymerization initiator) into 5 parts of water, and stirring became difficult owing to coagulated materials generated in course of dropping of the remainder of the emulsion A, and hence the polymerization was stopped.
• the initiator solution obtained by dissolving 0.1 part of ammonium persulfate (polymerization initiator) into 5 parts of water
• the temperature of the resultant solution was measured by a thermometer, and after an exothermic peak was observed, the remainder of the emulsion A was dropped by taking 4 hours at the inside temperature of 75° C., and the resultant system was aged for 2 hours at the same inside temperature of 75° C. to polymerize a monomer of the emulsion A and to form a copolymer (A).
• n-BMA Normal butyl methacrylate
• n-BA Normal butyl acrylate
• UVA1 [Formula VIII]
• HALS1 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine
• HALS2 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine
• Adeka Reasoap SR-10 reactive anion type surfactant (trade name, manufactured by Asahi Denka Kogyo K.K.)
• Adeka Reasoap ER-30 reactive nonion type surfactant (trade name, manufactured by Asahi Denka Kogyo K.K.)
• Latemul B-118E nonreactive anion type surfactant (trade name, manufactured by Kao Corporation)
• Nonipol 200 nonreactive nonion type surfactant (trade name, manufactured by Sanyo Chemical Industries, Ltd.)
• NDM Normal dodecyl mercaptan
• the weather resistance improvers for water-based paints of the present examples can realize conspicuous improvement in weather resistance when they are added to other water-based paints, as well as they are excellent in mechanical stability, storage stability and polymerization stability.
• the weather resistance improvers for water-based paints of the comparative examples are not excellent in polymerization stability or storage stability, and are insufficient in at least one characteristics of capability for improving weather resistance, water resistance, coloring property and pigment dispersibility, even if they are polymerizable, when they are added to other water-based paints as the weather resistance improvers for water-based paints.
• the weather resistance improver for water-based paints of the present invention is also useful as a weather resistance improver for water-based paints, which is excellent in mechanical stability and storage stability and has conspicuous capability for improving weather resistance.
• thermoplastic resins Various evaluations of the weather resistance improver for thermoplastic resins were carried out by the following methods.
• a plate molded article of 100 mm ⁇ 100 mm ⁇ 2 mm was made according to a compounding ratio shown in the following Table 9 using “ACRYPET MD” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.) as a base thermostatic resin.
• ACRYPET MD trade name, manufactured by Mitsubishi Rayon Co., Ltd.
• SANOL LS-770 trade name, manufactured by Sankyo Lifetech Co., Ltd.
• the initial mass average molecular mass (Mw) of “ACRYPET MD” was 92,000.
• a weather resistance improver for thermoplastic resins was kept at 20° C. for a day, and after that, an organoleptic examination was carried out at 20° C. The following standard was used for judgement.
• the test was carried out for 3,000 hours using a sunshine carbon weatherometer (manufactured by Suga test instruments Co., Ltd., “WEL-SUN-HC-B type” weather meter (black panel temperature: 63 ⁇ 3° C.; cycle of raining: 12 minutes and irradiation: 48 minutes)), and color difference (hereinafter, expressed as “ ⁇ E”) and molecular mass were measured, and the results were judged according to the following standard.
• ⁇ E color difference
• the temperature of the resultant solution was measured by a thermometer, and after an exothermic peak was observed, the remainder of the emulsion A was dropped by taking 4 hours at the inside temperature of 75° C., and the resultant system was aged for 2 hours at the same inside temperature of 75° C. to polymerize a monomer of the emulsion A and to form a copolymer emulsion.
• the concentration of the resultant dispersed emulsion was adjusted to 1% and average particle diameter was measured at 25° C. using “Fiber-Optics Particle Analyzer with Autosampler FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.
• the average particle diameter of cumulant analysis obtained by the measurement was adopted as a primary particle diameter.
• the dispersed emulsion cooled to room temperature was spray dried with a spray dryer (“L-8 type”, manufactured by Ohkawara Kakohki Co., Ltd.) under the conditions of the inlet temperature of 170° C., the outlet temperature of 60° C., and the number of revolution of atomizer of 25,000 rpm to recover solid matter as the polymeric weather resistance improver.
• the polymeric weather resistance improver thus obtained was observed by a scanning electron microscope, and an average of measured particle diameters of 20 particles was adopted as a secondary particle diameter.
• Example 31 The same procedure as in Example 31 was carried out for emulsion polymerization of emulsion (A) having the composition shown in Table 6, and the resultant dispersed emulsion was subjected to spray drying to recover solid matter using the same procedure as in Example 31.
• the results of evaluation are shown in Table 8.
• Example 31 The same procedure as in Example 31 was carried out for emulsion polymerization of emulsion (A) having the composition shown in Table 6, and the resultant dispersed emulsion was adjusted to 40° C., and introduced into the same amount of 1.5% calcium acetate aqueous solution of a coagulating agent while the mixture was stirred to coagulate the dispersed emulsion, and the resultant mixture was kept at 70° C. for 5 minutes to obtain a coagulated slurry. The resultant coagulated slurry was dehydrated and dried, and solid matter was recovered as a weather resistance improver for thermoplastic resins. The results of evaluation are shown in Table 8.
• Example 31 The same procedure as in Example 31 was carried out for emulsion polymerization of emulsion (A) having the composition shown in Table 6, and the resultant dispersed emulsion was subjected to spray drying to recover solid matter using the same procedure as in Example 31.
• the results of evaluation are shown in Table 8.
• Example 31 The same procedure as in Example 31 was carried out for preparation of emulsion (A) having the composition shown in Table 3 and for emulsion polymerization of the emulsion (A), however, aggregation and fixation of the system occurred after 10 minutes from the start of dropping of the emulsion (A) and the polymerization was stopped.
• n-BA Normal butyl acrylate
• HALS1 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine
• HALS2 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine “Pelex OT-P”: nonreactive anion type surfactant (trade name, manufactured by Kao Corporation)
• Alka Reasoap SR-10 reactive anion type surfactant (trade name, manufactured by Asahi Denka Kogyo K.K.)
• Alka Reasoap ER-30 reactive nonion type surfactant (trade name, manufactured by Asahi Denka Kogyo K.K.)
• NDM Normal dodecyl mercaptan
• the initial mass average molecular mass (Mw) based on standard polystyrene of “ACRYPET MD” used in Table 9 was 92,000.
• SANOL LS-770 trade name, manufactured by Sankyo Lifetech Co., Ltd.
• the test was carried out for 3,000 hours using a sunshine carbon weatherometer (manufactured by Suga test instruments Co., Ltd., “WEL-SUN-HC-B type” weather meter (black panel temperature: 63 ⁇ 3° C.; cycle of raining: 12 minutes and irradiation: 48 minutes)), and color difference (hereinafter, expressed as “ ⁇ E”) and molecular mass were measured, and the results were judged according to the following standard.
• ⁇ E color difference
• thermoplastic resins of the present examples do not have odor and can realize conspicuous improvement in weather resistance for long time when they are added to thermoplastic resins, as well as they are excellent in polymerization stability.
• the water-based resin compositions of the Comparative Examples have a problem of odor and are not excellent in polymerization stability, and are insufficient in at least one characteristics of compatibility, capability for improving weather resistance, water resistance, coloring property and retention of molecular mass, even if they are polymerizable, when they are added to other thermoplastic resins as the weather resistance improvers for thermoplastic resins.
• thermoplastic resin compositions obtained in the Examples 31 to 33 and the Comparative Examples 15, 17 and 18 were used as a weather resistance improver for solvent-based paints and evaluation was carried out. The results are shown in Table 10.
• Comparative Example 26 is an example in which a weather resistance improver for solvent-based paints or an ultraviolet light stabilizer is not compounded, and Comparative Example 26 is an example in which a nonreactive HALS (“SANOL LS-292” (trade name, manufactured by Sankyo Lifetech Co., Ltd.)) was used as an ultraviolet light stabilizer.
• SANOL LS-292 trade name, manufactured by Sankyo Lifetech Co., Ltd.
• a weather resistance improver for solvent-based paints or an ultraviolet light stabilizer was compounded at the rate shown in Table 10 to “BR-106” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.), and the resultant mixture was dissolved in toluene to obtain a solution with solid content of 45%.
• BR-106 trade name, manufactured by Mitsubishi Rayon Co., Ltd.
• KF-69 trade name, manufactured by Kao Corporation
• the resultant resin solution was diluted with a thinner having a 50/50 of toluene/butyl acetate composition to have the viscosity of 15 seconds in terms of “Ford Cup 4”, and filtrated using 300 mesh nylon screen to obtain a clear paint for evaluation.
• the clear paint thus obtained was coated on a steel plate treated with zinc phosphate treatment (steel plate treated with “Bondelite #100”, thickness: 0.8 mm, 70 mm ⁇ 150 mm) by spray coating to the extent that the thickness of the dried coating film became 50 ⁇ m, and kept at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for the tests of compatibility, water resistance, weather resistance and capability for improving weather resistance.
• thermoplastic resins of each Example of 38 to 40 and each Comparative Example of 15, 17 and 18 was compounded at the rate shown in Table 10 to “BR-106” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.), and the resultant mixture was dissolved in toluene to obtain a solution with solid content of 45%.
• the enamel paint thus obtained was coated on a steel plate treated with zinc phosphate treatment (steel plate treated with “Bondelite #100”, thickness: 0.8 mm, 70 mm ⁇ 150 mm) by spray coating to the extent that the thickness of the dried coating film became 50 ⁇ m, and kept at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for the tests of weather resistance, chalking and capability for improving weather resistance.
• Viscosity of a resin solution was measured according to the Gardner type viscosity-measuring method described in JIS-K5600-2-2, 4, in which viscosity is obtained from an ascension rate of a bubble as compared with a standard viscosity tube.
• Gloss (unit: degree) was measured with a polarized light glossmeter “VG-2000” manufactured by Nippon Denshoku Industries Co., Ltd. Gloss of a sample before the test is shown in Table 8 as an initial gloss.
• a glass plate was coated with a clear paint using a 8 mil applicator, and dried at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for evaluation of compatibility.
• the state of the coating film was checked by visual inspection and judged according to the following standard.
• a glass plate was coated with a clear paint using a 8 mil applicator, and dried at a room temperature for 1 hour and subjected to forced drying at 80° C. for 1 hour to obtain a coated plate for evaluation of water resistance. Subsequently, the coated plate was soaked in water at a room temperature (about 20° C.) for 1 week. Whitening of the coating film right after the plate was taken out was checked by visual inspection and judged according to the following standard.
• the test was carried out with a test plate using a sunshine carbon weatherometer (manufactured by Suga test instruments Co., Ltd., “WEL-SUN-HC-B type” weather meter (black panel temperature: 63 ⁇ 3° C.; cycle of raining: 12 minutes and irradiation: 48 minutes)).
• Time at which gloss retention of the test plate became less than 70% was checked at every 500 hours in the first 2,000 hours and at every 1,000 hours from 2,000 hours, and was adopted as a retention time of weather resistance of the test plate sample, and the weather resistance of the test plate sample was judged according to the following standard.
• a state of chalking of a coating film after an accelerated test of 3,000 hours was checked by visual inspection and judged according to the following standard.
• the resin compositions of the Comparative Examples are out of the specified compositional range of the present invention, and have a problem in polymerization stability, and are insufficient in at least one characteristics of compatibility, capability for improving weather resistance, water resistance and retention of molecular mass, even if they are polymerizable, when they are added to other solvent-based paints as the weather resistance improvers for solvent-based paints.
• the weather resistance improver for solvent-based paints of the present invention is excellent in polymerization stability and also useful as a weather resistance improver for solvent-based paints, which has conspicuous capability for improving weather resistance.
• the water-based resin composition of the present invention can realize weather resistance for a long time as a water-based paint and can be used for a surface finish of various materials such as cement mortars, slate plates, plaster boards, extruded molded articles, foam concretes, metal, glass, ceramic tile, asphalt, wood, water resistant rubber, plastics and calcium-silicate base materials.
• weather resistance improver of the present invention By adding a weather resistance improver of the present invention to a water-based paint, weather resistance of a coating film of the water-based paint can be improved for a long time.
• a resin composition obtained by recovering solid matter in the water-based resin composition of the present invention can be used effectively as a weather resistance improver for thermoplastic resins, which can improve a weather resistance for a long time, by adding to an acrylic resin, a vinyl chloride resin, a polyethylene resin, a polypropylene resin, a polystyrene resin, an ABS resin, a polyamide resin, a polyester resin, a polycarbonate resin or the like which is used for interiors or exteriors of automobiles, exterior building materials, films for agricultural application, coatings for electrical wire and the like.
• the resin composition obtained by recovering solid matter in the water-based resin composition of the present invention can also be used as a weather resistance improver for solvent-based paints, which can improve a weather resistance, by adding the resin composition to solvent-based paints which are used for surface finish of various materials.

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